1、Designation: D 4252 89 (Reapproved 2003)Standard Test Methods forChemical Analysis of Alcohol Ethoxylates and AlkylphenolEthoxylates1This standard is issued under the fixed designation D 4252; the number immediately following the designation indicates the year oforiginal adoption or, in the case of
2、revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 These test methods cover the various test methods usedto evaluate those properties pertinent to
3、 the characterization ofalcohol ethoxylates and alkylphenol ethoxylates with respect tosuitability for desired uses.1.2 The procedures for sampling and analysis appear in thefollowing order:SectionsSamplingLiquids 6Solids 7Methods of Chemical AnalysisWater or moisture 8Refractive index 9 and 10pH 11
4、Acidity or basicity 12 and 13Hydroxyl number 14-20Cloud point 21Iodine number 22Ash 23Iron 24Ethylene oxide content 25Polyethylene glycols 26-321.3 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standa
5、rd to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Material SafetyData Sheets are available for reagents and materials. Reviewthem for hazards prior to usage. Specific hazard statementsappear in Section 5 and Note 1 and N
6、ote 3.2. Referenced Documents2.1 ASTM Standards:D 459 Terminology Relating to Soaps and Other Deter-gents2D 482 Test Method for Ash from Petroleum Products3D 1068 Test Methods for Iron in Water4D 1172 Test Method for pH of Aqueous Solutions of Soapsand Detergents2D 1193 Specification for Reagent Wat
7、er4D 1209 Test Method for Color of Clear Liquids (Platinum-Cobalt Scale)5D 1218 Test Method for Refractive Index and RefractiveDispersion of Hydrocarbon Liquids3D 1613 Test Method for Acidity in Volatile Solvents andChemical Intermediates Used in Paint, Varnish, Lacquer,and Related Products5D 1959 T
8、est Method for Iodine Value of Drying Oils andFatty Acids6D 2024 Test Method for Cloud Point of Nonionic Surfac-tants2D 2959 Test Method for Ethylene Oxide Content of Poly-ethoxylated Surfactants2E 180 Practice for Determining the Precision of ASTMMethods for Analysis and Testing of Industrial Chemi
9、cals7E 200 Practice for Preparation, Standardization, and Stor-age of Standard Solutions for Chemical Analysis7E 203 Test Method for Water Using Karl Fischer Reagent7E 394 Test Method for Iron in Trace Quantities Using the1,10-Phenanthroline Method73. Significance and Use3.1 Alcohol ethoxylates and
10、alkylphenol ethoxylates areimportant surfactants in household and industrial cleaners.They may be used as either nonionic surfactants or sulfated andused as anionic surfactants. Careful control of the ethoxylatecharacteristics is desired as variations may result in eitherdesirable or undesirable end
11、-use properties.4. Purity of Reagents4.1 Reagent-grade chemicals shall be used in all tests.Unless otherwise indicated, it is intended that all reagents shallconform to the specifications of the Committee on Analytical1These test methods are under the jurisdiction of ASTM Committee D12 onSoaps and O
12、ther Detergents and are the direct responsibility of Subcommittee 12.12on Analysis of Soaps and Synthetic Detergents.Current edition approved May 26, 1989. Published July 1989. Originallypublished as D 4252 83. Last previous edition D 4252 88.2Annual Book of ASTM Standards, Vol 15.04.3Annual Book of
13、 ASTM Standards, Vol 05.01.4Annual Book of ASTM Standards, Vol 11.01.5Annual Book of ASTM Standards, Vol 06.04.6Annual Book of ASTM Standards, Vol 06.03.7Annual Book of ASTM Standards, Vol 15.05.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, Unit
14、ed States.Reagents of the American Chemical Society, where suchspecifications are available.8Other grades may be used, pro-vided it is first ascertained that the reagent is of sufficientlyhigh purity to permit its use without lessening the accuracy ofthe determination.4.2 Unless otherwise indicated,
15、 references to water shall beunderstood to mean Type III reagent water conforming toSpecification D 1193.5. Safety Precautions5.1 All reagents and chemicals should be handled with care.Before using any chemical, read and follow all safety precau-tions and instructions on the manufacturer label. Clea
16、n up anyspill immediately. For information on cleaning up spills refer tothe Laboratory Disposal Manual, Manufacturing ChemistsAssociation, Washington, DC.SAMPLING6. Liquids6.1 Thoroughly mix the sample before sampling. If a solidlayer or crystals have formed on the bottom of the bottle, meltin an o
17、ven or water bath at 55C and mix well before sampling.7. Solids7.1 Melt in an oven or water bath at 55C and mix wellbefore sampling. If it is necessary to heat at temperatures above60C, replace the gas cap with an inert gas, such as oxygen-freenitrogen, helium, or argon before heating.WATER OR MOIST
18、URE8. Procedure8.1 Determine water or moisture in accordance with TestMethod E 203.REFRACTIVE INDEX9. Procedure9.1 Measure the refractive index at 50C in accordance withTest Method D 1218.10. Precision10.1 The following criteria should be used for judging theacceptability of results:9,1010.1.1 Repea
19、tability (Single Analyst)The standard devia-tion of results (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be0.00021 units absolute at 36 df. Two such averages should beconsidered suspect (95 % confidence level) if they differ bymore than 0.000
20、59 units absolute.10.1.2 Reproducibility (Multilaboratory)The standard de-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been estimated to be0.00059 units absolute at 7 df. Two such averages should beconsidered suspect (95 % confidence level)
21、if they differ bymore than 0.0020 units absolute.10.1.3 Checking Limits for DuplicatesReport the refrac-tive index of the sample to the nearest 0.0001. Duplicate runsthat agree within 0.00025 units are acceptable for averaging(95 % confidence level).pH11. Procedure11.1 Determine the pH in accordance
22、 with Test MethodD 1172, except prepare the solution by transferring 1 6 0.001g of the sample to a 100 mL volumetric flask and diluting inaccordance with Test Method D 1172. Measure the pH 10 minafter diluting the sample solution to volume.ACIDITY OR BASICITY12. Procedure12.1 Determine acidity or ba
23、sicity in accordance with TestMethod D 1613 using a 3+1 solution of isopropyl alcohol andwater as the solvent and a 10-g sample.13. Precision13.1 The following criteria should be used for judging theacceptability of results:10,1113.1.1 Repeatability (Single Analyst)The standard devia-tion of results
24、 (each the average of duplicates), obtained by thesame analyst on different days, has been estimated to be 0.017meq/100 g at 27 df. Two such averages should be consideredsuspect (95 % confidence level) if they differ by more than0.049 meq/100 g.13.1.2 Reproducibility (Multilaboratory)The standard de
25、-viation of results (each the average of duplicates), obtained byanalysts in different laboratories, has been established to be0.12 meq/100 g at 5 df. Two such averages should beconsidered suspect (95 % confidence level) if they differ bymore than 0.44 meq/100 g.13.1.3 Checking Limits for Duplicates
26、Report the acidityor basicity of the sample to the nearest 0.05 meq/100 g.Duplicate runs that agree within 0.051 meq/100 g are accept-able for averaging (95 % confidence level).HYDROXYL NUMBER14. Terminology14.1 Definition:8Reagent Chemicals, American Chemical Society Specifications, AmericanChemica
27、l Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockvil
28、le,MD.9The precision estimates are based on an interlaboratory study on ALFONICt1412-60, MAKONt-10, NEODOLt 25-9, PLURONICt 25R1, and TERGITOL15-S-3 by nine laboratories.10Statistical analysis was performed in accordance with Practice E 180 fordeveloping precision estimates. Data supporting the prec
29、ision statements are on fileat ASTM Headquarters, 100 Barr Harbor Drive, West Conshohocken, PA 19428 asRR: D12-1004.11The precision estimates are based on an interlaboratory study on ALFONICt1412-60, MAKONt-10, NEODOLt 25-9, PLURONICt 25R1 and TERGITOLt15-S-3 by six laboratories.D 4252 89 (2003)214.
30、1.1 hydroxyl numberthe number of milligrams of po-tassium hydroxide equivalent to the hydroxyl content of1gofsample.15. Summary of Test Method15.1 The hydroxyl groups are esterified by reaction withphthalic anhydride in a pyridine medium at the temperature ofreflux of the mixture. After cooling, the
31、 excess of phthalicanhydride is hydrolyzed with water and the phthalic acidformed is titrated to the phenolphthalein end point withstandard sodium hydroxide solution. The hydroxyl content iscalculated from the difference in titration of the blank and ofthe sample solution.16. Apparatus16.1 Reflux As
32、sembly, consisting of a reflux condenser anda 250-mL Erlenmeyer flask, 24/40 standard taper joint withTFE-fluorocarbon sleeves.16.2 Buret, 50 mL, graduated in 0.1-mL intervals. Class Aor equivalent.16.3 Pipet, 25-mL capacity, Class A or equivalent.16.4 Insulating Pad,312 by 312 by 1 in., preferably
33、notasbestos.17. Reagents17.1 Pyridine, A. R.To be acceptable, each lot should passthe following quality test: Place7gofphthalic anhydride and50 mL of pyridine (Warningsee Note 1) in a glass-stopperedflask, shake vigorously until dissolved. Heat at 50 or 60C for30 min, allow to stand at room temperat
34、ure in the dark for 24h and then measure the Pt-Co color (Test Method D 1209). Thepyridine is acceptable if the color does not exceed 200.NOTE 1Warning: Avoid breathing pyridine vapors, as they are toxic.Dispose of pyridine wastes in a well ventilated hood.17.2 Sodium Hydroxide,(1N), carbonate free.
35、 Purchase orprepare, standardize, and store according to Practice E 200.17.3 Phthalic Anhydride ReagentDissolve 98 6 1gofphthalic anhydride in 700 mL of pyridine (Note 1), shake toeffect solution. Store in a brown bottle. Preferably, the solutionshould stand overnight before using. Prepare a fresh r
36、eagenteach week or more frequently if the Pt-Co color (Test MethodD 1209) exceeds a value of 200.17.4 Sodium Hydroxide (0.1 N)Purchase or prepare, stan-dardize, and store according to Practice E 200.17.5 Hydrochloric Acid (0.1 N)Purchase or prepare bydiluting 8.3 mL of concentrated hydrochloric acid
37、 to 1 L withdistilled water. Standardize and store according to PracticeE 200.17.6 Phenolphthalein Indicator SolutionDissolve1gofphenolphthalein in 100 mL of pyridine.17.7 Isopropyl Alcohol,A.R.18. Procedure18.1 Weigh into a clean and dry 250-mL Erlenmeyer flaskwith ground glass joint to the nearest
38、 0.1 mg an amount ofsample calculated by means of the following equation but donot use more than 10 g of sample:Amount of Sample, g 5MF 3 100(1)where:M = molecular weight of sample andF = number of hydroxyl groups per molecule.18.2 Pipet accurately 25 mL of phthalic anhydride reagentinto the flask a
39、nd swirl to effect solution. Add two boilingchips, attach a dry reflux condenser with a ground glass jointfitted with a TFE-fluorocarbon sleeve to the flask, and refluxfor1honanelectric hotplate.18.3 Turn off the hotplate and insert an insulated padbetween the flask and the hot plate. Allow to cool
40、for 20 min.Wash down the condenser, first with 25 mL of pyridine andthen with 25 mL of water.18.4 Remove the flask from the condenser. Add 4 or 5 dropsof phenolphthalein indicator to the flask and titrate withstandard 1 N sodium hydroxide solution to a faint pink endpoint (Note 2).18.5 Make a blank
41、determination following 18.2-18.4.NOTE 2It is essential that the sample titration requires at least threefourths of the blank titration. The difference between the two titrationsshould be of the order of 10 mL. If this is not the case the sample sizeshould be adjusted accordingly and the analysis re
42、run.18.6 Determine the free acidity or free alkalinity as de-scribed in Section 12 or as follows: To 25 mL of a 3 + 1isopropyl alcohol/water mixture in a 250-mL Erlenmeyer flaskadd 2 to 3 drops of phenolphthalein indicator solution andtitrate with standard 0.1 N sodium hydroxide solution to a faintp
43、ink. Accurately weigh 10 to 20 g of sample and add to thecontents of the flask.18.7 If the solution is colorless titrate with standard 0.1 Nsodium hydroxide solution to a faint pink. If the solution ispink titrate with standard 0.1 N hydrochloric acid to justcolorless.19. Calculations19.1 Calculate
44、the hydroxyl number from the followingequations:19.1.1 For samples containing free acidity:Hydroxyl Number, mg KOH/g 5FB 2 S!NW1C 3 N1W1G3 56.1(2)19.1.2 For samples containing free alkalinity:Hydroxyl Number, mg KOH/g 5FB 2 S!NW2C 3 N1W1G3 56.1(3)where:B = volume of 1 N sodium hydroxide solution req
45、uiredfor blank titration (18.5), mL,S = volume of 1 N sodium hydroxide solution requiredfor sample titration (18.4), mL,N = normality of 1 N sodium hydroxide solution,W = weight of sample taken (18.1), g,D 4252 89 (2003)3C = volume of 0.1 N sodium hydroxide/hydrochloric acidrequired for acidity/alka
46、linity titration (18.7), mL,N1= normality of 0.1 N sodium hydroxide/hydrochloricacid used for acidity/alkalinity titration (18.7), andW1= weight of sample used for acidity/alkalinity titration(18.6), g.19.2 Calculate the apparent molecular weight from thefollowing equation:Apparent Molecular Weight
47、556,100H3 F (4)where:H = hydroxyl number (mg KOH/g sample).F = number of hydroxyl groups per molecule.20. Precision20.1 The following criteria should be used for judging theacceptability of the results:10,1220.1.1 Repeatability (Single Analyst)The standard devia-tion of results (each the average of
48、duplicates), obtained by thesame analyst on different days, has been estimated to be 1.10 %relative at 30 df. Two such averages should be consideredsuspect (95 % confidence level) if they differ by more than3.18 % relative.20.1.2 Reproducibility (Multilaboratory)The standard de-viation of results (e
49、ach the average of duplicates), obtained byanalysts in different laboratories, has been estimated to be1.80 % relative at 6 df. Two such averages should be consid-ered suspect (95 % confidence level) if they differ by more than6.21 % relative.20.1.3 Checking Limits for DuplicatesReport the hy-droxyl number of the sample to the nearest unit. Duplicate runsthat agree within 2.03 % relative are acceptable for averaging(95 % confidence level).CLOUD POINT21. Procedure21.1 Determine the cloud point in accordance with TestMethod D 2024.IODINE NUMBER22. Procedure
